CN112375324B - HIPS (high impact polystyrene) composite material as well as preparation method and application thereof - Google Patents
HIPS (high impact polystyrene) composite material as well as preparation method and application thereof Download PDFInfo
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- CN112375324B CN112375324B CN202011369958.XA CN202011369958A CN112375324B CN 112375324 B CN112375324 B CN 112375324B CN 202011369958 A CN202011369958 A CN 202011369958A CN 112375324 B CN112375324 B CN 112375324B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L51/04—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to rubbers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2207/00—Properties characterising the ingredient of the composition
- C08L2207/06—Properties of polyethylene
- C08L2207/062—HDPE
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2207/00—Properties characterising the ingredient of the composition
- C08L2207/06—Properties of polyethylene
- C08L2207/066—LDPE (radical process)
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Abstract
The invention provides a HIPS composite material and a preparation method and application thereof, wherein the composite material comprises the following components in parts by mass: HIPS resin: 30-60 parts; styrene oligomer: 0.5-2 parts; HDPE resin: 10-35 parts; LDPE resin: 10-35 parts; EVA resin: 2-10 parts; filling materials: 2-10 parts; a toughening agent: 5-10 parts; processing aid: 0.5 to 1.5 portions. The PS composite material has the characteristics of low density, high toughness and low stress cracking.
Description
Technical Field
The invention belongs to the field of modified plastics, and particularly relates to a HIPS (high impact polystyrene) composite material as well as a preparation method and application thereof.
Background
Styrene (PS) and Polyethylene (PE) materials are common polymers, and are widely used as important varieties of general plastics, and are commonly used in the fields of home appliances, electronic appliances, OA office equipment, and the like. The polystyrene material has the advantages of easy molding, good rigidity, easy dyeing and the like. But the PS material has insufficient impact toughness and poor environmental stress cracking resistance, and limits the application range of the PS material. The PE material has the characteristics of low density, good toughness, excellent solvent resistance, good barrier property and low price, but has the defects of low rigidity and poor dimensional stability.
Because the impact toughness of the conventional PS material is limited, the requirement cannot be met when the product with high toughness is applied, for example, the PS material can be applied to packaging products which can adapt to various harsh environments outdoors, and needs to be subjected to toughening treatment. The method for toughening PS by using the rubber elastomer to improve the toughness is generally used, but the rubber elastomer for toughening contains an unsaturated double bond structure, so that an aging reaction is easy to occur, and the rubber elastomer is easy to become brittle and stress-cracked in a severe cold environment. Polyethylene (PE) material is a crystalline material, and once the material reaches a melting point, the fluidity of the material is very good, a melt is molded more smoothly in a mold, the stress is small, and the probability of stress cracking is reduced.
The PS/PE alloy material combines the excellent performances of the two materials, and can be applied to outdoor large-scale packing box products with high requirements on low density, high toughness and low stress cracking.
Chinese patent CN 109161079B discloses a PE/PS/SEBS-g-MAH composite material and a preparation method thereof, and the composite material integrates the comprehensive properties of a plurality of resins and can be applied to the field of foaming materials. However, no outstanding improvement research is carried out on the aspects of high toughness and reduction of stress cracking of the material, and the high price of the graphene component in the material can limit the application and popularization in a wide range. Meanwhile, the composite material contains too few components for stabilizing the size of the material and preventing warping, and the dimensional stability of the material is easily reduced due to the addition of the crystalline material PE in a large proportion. The SEBS-g-MAH component is added in a large amount, the existing smell of Maleic Anhydride (MAH) is large, and the produced packaging product can generate smell influence on the packaged objects.
Disclosure of Invention
In view of the above, the invention provides a HIPS composite material, a preparation method and an application thereof, aiming at overcoming the defects in the prior art.
In order to achieve the purpose, the technical scheme of the invention is realized as follows:
the HIPS composite material comprises the following components in parts by mass:
HIPS resin: 30-60 parts;
styrene oligomer: 0.5-2 parts;
HDPE resin: 10-35 parts;
LDPE resin: 10-35 parts;
EVA resin: 2-10 parts;
filling materials: 2-10 parts;
a toughening agent: 5-10 parts;
processing aid: 0.5 to 1.5 portions.
Preferably, the HIPS resin has a melt flow rate of 3 to 5g/10min (200 ℃ C., 5 kg).
Preferably, the molecular weight of the styrene oligomer is 800-1300. More preferably, the styrene oligomer is a styrene oligomer having model number AMS-120 manufactured by Wuxi Kaishao advanced modified materials Co.
Preferably, the filler is talcum powder with a chemically treated surface.
Preferably, the toughening agent is a styrenic elastomer, preferably an oil-extended SBS elastomer. The preparation process comprises the following steps: firstly, the dispersant with stronger polarity is dissolved in the silicone oil and then is absorbed on SBS to complete oil filling.
Preferably, the content of VA in the EVA resin is 35%.
Preferably, the processing aid is one or more of a main antioxidant, an auxiliary antioxidant, an internal lubricant and an external lubricant.
Preferably, the main antioxidant or the auxiliary antioxidant is a compound of a hindered phenol antioxidant and a thioether phosphite ester auxiliary antioxidant; the internal lubricant or the external lubricant is one or more than two of stearic acid lubricant, polyethylene lubricant, ester lubricant, paraffin lubricant or amide lubricant.
Preferably, the PS composite material also comprises a processing aid accounting for 0.5-1.5% of the total mass of the raw materials;
the invention also provides a preparation method of the PS composite material, which comprises the following steps:
freezing and grinding the LDPE resin and the EVA resin, uniformly mixing the powder with other raw materials except the oil-filled SBS elastomer, feeding the mixture from a main feeding port of an extruder, weighing the oil-filled SBS elastomer through side feeding, and feeding the oil-filled SBS elastomer into a screw cylinder of the extruder from the side; the PS composite material with the characteristics of low density, high toughness and low stress cracking is obtained after raw materials are melted, extruded and granulated in an extruder.
Preferably, the extruder is preferably a twin-screw extruder, and the melting is performed at 170-210 ℃.
The invention also provides an application of the HIPS composite material in preparing outdoor packaging products.
Compared with the prior art, the invention has the following advantages:
(1) the PS composite material has the characteristics of low density, high toughness and low stress cracking, and the oil-filled SBS elastomer is used as the toughening agent, so that the impact toughness of the composite material is improved, the material can keep better fluidity, and the condition that the material is subjected to stress cracking due to extra stress caused by injection molding under the condition of high pressure is avoided. And the compatibility of PS phase and PE phase is improved by adding EVA resin, and the interface strength is improved, thereby improving the mechanical property of the material.
(2) According to the PS composite material, the PE resin component is added, so that the toughness of the material can be improved, the density of the material can be reduced, meanwhile, the PE crystalline material is very good in fluidity after being melted, so that the internal stress can be reduced, and the effects of low density and low stress cracking are achieved. The PE material has lighter density, can reduce the density of the composite material, reduce the gram weight of the plastic product and achieve good weight reduction effect. The styrene oligomer has very good fluidity and can also play a role in reducing stress.
(3) Before adding resin, the PS composite material needs to carry out freezing and grinding treatment on LDPE resin and EVA resin to obtain raw materials with larger specific surface area, and the raw materials are more fully fused in the mixing, melting and mixing processes. Through the pretreatment and the compatibilization process, the PS phase and the PE phase are more fully compatible, and the probability of stress cracking is reduced.
(4) The PS composite material is added through a feeding port at the rear end side of a double-screw extruder when the oil-filled SBS elastomer is added. The oil-filled SBS elastomer has higher rubber content, and the addition of the feeding port at the rear end side reduces the shearing time of the elastomer in an extruder, so that the toughening effect is better. Meanwhile, the SBS elastomer which is relatively low in temperature resistance and is filled with oil is added at the section of the screw cylinder, so that the processing temperature of the front section of the screw cylinder is higher, the viscosity of the melt is greatly reduced, and more stress is avoided.
(5) After the talcum powder is added into the PS composite material, the rigidity of the material can be improved, and the defect that PE is softer is overcome. Meanwhile, the talcum powder surface is chemically treated, and the surface is provided with more organic matters and chemical functional groups, so that the inorganic particles are better fused with various plastics, and the toughness can be better maintained besides the improvement of the rigidity.
Detailed Description
Unless defined otherwise, technical terms used in the following examples have the same meanings as commonly understood by one of ordinary skill in the art to which the present invention belongs. The test reagents used in the following examples, unless otherwise specified, are all conventional biochemical reagents; the experimental methods are conventional methods unless otherwise specified.
The invention will be described in detail with reference to the following examples.
The sources of the raw materials in the examples and comparative examples are as follows:
HIPS comes from Qimei company, and the model is PH-88;
the styrene oligomer is from the No-Sn high-tech modified materials company, model AMS-110, AMS-120, AMS-130, wherein the molecular weight of AMS-120 is 800-1300, the molecular weight of AMS-110 is below 800, and the molecular weight of AMS-130 is above 1300;
LDPE is available from Daqing petrochemical company and has the model number of LDPE 2426;
HDPE available from Exxon Mobil corporation, type HDPE HMA 025;
the toughening agent is from Liangrong chemical industry company, and the type is SBS 1546;
the EVA resin is from DuPont and has the model number of 150W;
the filler is from Longsheng Huamei company, and has model number AH-1250N 6;
the antioxidant is from Basf corporation;
lubricants were from queen corporation;
in the following examples, the processing conditions for melt extrusion in an extruder are as follows: the temperature of the first zone is 170-.
Examples 1 to 5
The PS composite material with the characteristics of low density, high toughness and low stress cracking is shown in a table 1, and the preparation method comprises the following steps:
freezing and grinding the LDPE resin and the EVA resin, uniformly mixing the powder with other raw materials except the oil-filled SBS elastomer, feeding the mixture from a main feeding port of an extruder, weighing the oil-filled SBS elastomer through side feeding, and feeding the oil-filled SBS elastomer into a screw cylinder of the extruder from the side; the PS composite material with the characteristics of low density, high toughness and low stress is obtained after raw materials are melted, extruded and granulated in an extruder.
The pellets were injection molded into corresponding test specimens for testing, the test results are shown in Table 2.
Comparative examples 1 to 5
The PS composite material has the raw material formula shown in Table 1, and the preparation method comprises the following steps:
freezing and grinding the LDPE resin and the EVA resin, uniformly mixing the LDPE resin and the EVA resin with other raw materials except the toughening agent, feeding the mixture from a main feeding port of an extruder, weighing the toughening agent through side feeding, and feeding the toughening agent into a screw cylinder of the extruder; the raw materials are melted in an extruder, extruded, granulated and dried. The components are all in the prior art. The toughener of comparative example 4 was selected from a conventional commercially available SBS elastomer available from Liangrong chemical industries as SBS 1546.
TABLE 1 raw material formulation (in parts by mass) of PS composites of examples and comparative examples
TABLE 2 test data for PS composites of examples and comparative examples
Note: XX-very poor; x-is poor; excellent-better; very good; very excellent; very excellent very good
In example 1, compared with comparative example 1 and example 4, compared with comparative example 3, AMS-120 can obviously improve the stress cracking situation compared with AMS-110 and AMS-130, and it can be seen that the styrene oligomer with the molecular weight of 800-1300 selected by the invention is more excellent in the overall mechanical property and stress cracking resistance of the material, and the AMS-120 compatibility is better in both the aspects of processability and fluidity.
Compared with example 4, the EVA resin with higher VA content is not added in the comparative example 2, and the interface strength is improved in the example 4, so that the overall mechanical property of the material is improved.
In comparative example 4, no flexibilizer of oil-extended SBS elastomer was added, and the impact toughness of the obtained composite material was poor.
In conclusion, the toughening agent of the EVA resin with high VA content and the oil-extended SBS elastomer and the styrene oligomer with the molecular weight of 800-1300 are selected and used in a compound way with the HIPS resin, the HDPE resin and the LDPE resin in a reasonable ratio, so that the obtained material has excellent overall mechanical property and the probability of stress cracking is reduced.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and should not be taken as limiting the invention, so that any modifications, equivalents, improvements and the like, which are within the spirit and principle of the present invention, should be included in the scope of the present invention.
Claims (10)
1. A HIPS composite characterized by: the paint comprises the following components in parts by mass:
HIPS resin: 30-60 parts;
styrene oligomer: 0.5-2 parts;
HDPE resin: 10-35 parts;
LDPE resin: 10-35 parts;
EVA resin: 2-10 parts;
filling materials: 2-10 parts;
a toughening agent: 5-10 parts;
processing aid: 0.5-1.5 parts;
the molecular weight of the styrene oligomer is 800-1300;
the toughening agent is an oil-extended SBS elastomer.
2. The HIPS composite of claim 1, wherein: the melt flow rate of the HIPS resin is 3-5g/10min at the temperature of 200 ℃ and under the condition of 5 kg.
3. The HIPS composite of claim 1, wherein: the styrene oligomer is a styrene oligomer of model AMS-120 produced by Wuxi Jiasheng high-new modified materials Co.
4. The HIPS composite of claim 1, wherein: the filler is talcum powder with chemically treated surface.
5. The HIPS composite of claim 1, wherein: the content of VA in the EVA resin is 35%.
6. The HIPS composite of claim 1, wherein: the processing aid is one or more of a main antioxidant, an auxiliary antioxidant, an internal lubricant and an external lubricant.
7. The HIPS composite of claim 6, wherein: the main antioxidant or the auxiliary antioxidant is compounded by hindered phenol antioxidant and thioether phosphite ester auxiliary antioxidant; the internal lubricant or the external lubricant is one or more than two of stearic acid lubricant, polyethylene lubricant, ester lubricant, paraffin lubricant or amide lubricant.
8. A process for the preparation of the HIPS composite of any of claims 1 to 7, wherein: the method comprises the following steps: freezing and grinding HIPS resin, then uniformly mixing the HIPS resin with LDPE resin, EVA resin, styrene oligomer, HDPE resin, filler and processing aid, then feeding the mixture from a main feeding port of an extruder, weighing the oil-filled SBS elastomer through side feeding, and feeding the elastomer into a screw cylinder of the extruder; the PS composite material with the characteristics of low density, high toughness and low stress cracking is obtained after raw materials are melted, extruded and granulated in an extruder.
9. The method of making the HIPS composite of claim 8, wherein: the extruder is a double-screw extruder, and the melting is performed at the temperature of 170-210 ℃.
10. Use of the HIPS composite of any of claims 1-7 in the preparation of outdoor packaging products.
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| CN114196127B (en) * | 2021-12-06 | 2023-06-13 | 天津金发新材料有限公司 | Modified polystyrene composite material and preparation method and application thereof |
| CN114591587B (en) * | 2022-02-25 | 2023-09-05 | 成都金发科技新材料有限公司 | Polystyrene composite material and preparation method thereof |
| CN115612238B (en) * | 2022-11-08 | 2023-08-29 | 武汉金发科技有限公司 | Polystyrene-polyethylene alloy material and preparation method and application thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2018121167A1 (en) * | 2016-12-27 | 2018-07-05 | 金发科技股份有限公司 | Polystyrene composition and application thereof |
| CN109553874A (en) * | 2018-12-26 | 2019-04-02 | 天津金发新材料有限公司 | A kind of low temperature resistant, light aging resisting material flame retardant polystyrene composite, preparation method and applications |
| CN111019257A (en) * | 2019-12-13 | 2020-04-17 | 天津金发新材料有限公司 | High-toughness, heat-resistant and wear-resistant PS material and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2018121167A1 (en) * | 2016-12-27 | 2018-07-05 | 金发科技股份有限公司 | Polystyrene composition and application thereof |
| CN109553874A (en) * | 2018-12-26 | 2019-04-02 | 天津金发新材料有限公司 | A kind of low temperature resistant, light aging resisting material flame retardant polystyrene composite, preparation method and applications |
| CN111019257A (en) * | 2019-12-13 | 2020-04-17 | 天津金发新材料有限公司 | High-toughness, heat-resistant and wear-resistant PS material and preparation method thereof |
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